WO2008041348A1

WO2008041348A1 - Polyisocyanate composition and method for producing hard polyurethane foam by using the composition

Info

Publication number: WO2008041348A1
Application number: PCT/JP2007/000999
Authority: WO
Inventors: Akira Sugano; Toshiyuki Anzai; Kunio Hirata
Original assignee: Nippon Polyurethane Industry Co., Ltd.
Priority date: 2006-09-29
Filing date: 2007-09-13
Publication date: 2008-04-10
Also published as: JP2008081702A

Abstract

Disclosed is a polyisocyanate composition which enables to obtain a hard polyurethane foam which is excellent in storage stability in an ultra-low temperature atmosphere, for example at -5˚C, while exhibiting excellent adhesion to an ultra-low temperature object, for example at -5˚C. Also disclosed is a method for producing a hard polyurethane foam by using such a polyisocyanate composition. Specifically disclosed is a polyisocyanate composition composed of a polymeric MDI, a ricinoleic acid alkyl ester, a silicone foam control agent and a dialkylglycol ether.

Description

Specification

Polyisocyanate composition and method for producing rigid polyurethane foam using the composition

Technical field

The present invention relates to a polyisocyanate composition and a method for producing a rigid polyurethane foam using the composition. More specifically, for example, it is possible to provide a rigid polyurethane foam that has excellent storage stability in an ultra-low temperature atmosphere of, for example, 5 ° C, and also has excellent adhesion to an ultra-low temperature substrate of, for example, -5 ° C. The present invention relates to a polyisocyanate composition, and a method for producing a rigid polyurethane foam using the polyisocyanate composition. In the present invention, “rigid polyurethane foam” is a concept including “isocyanurate-modified polyurethane foam” unless otherwise specified.

Background art

[0002] Conventionally, rigid polyurethane foam has been widely used as a heat insulating material for refrigerators, freezer warehouses, building materials, etc., and for spray applications.

[0003] The polyisocyanate used in the production of rigid polyurethane foam includes polymeric MDI including diphenylmethane diisocyanate (hereinafter abbreviated as “MD I”) and MD I multinuclear condensate. (Polyphenylene polymethylene polyisocyanate) is used.

[0004] — On the other hand, as a foaming agent in the production of rigid polyurethane foam, from the viewpoint of preventing the destruction of the ozone layer, etc. ) 1, 1, 1, 3, 3_Pentafluoropropane (hereinafter abbreviated as “H FC_245 fa”), 1, 1, 1, 3, 3_ Hydrofluorocarbons such as pentafluorobutane (hereinafter abbreviated as “HF C-365m fc”) are beginning to be used.

[0005] From the same viewpoint as above, only water is used as the blowing agent (complete) A rigid polyurethane foam with water foaming formula is also introduced.

[0006] However, hide mouth fluorocarbons and water used as foaming agents are used as urethane raw materials (isocyanate compositions and polyol compositions) as compared to conventional (hide mouth) black mouth fluorocarbons. ) And inferior in uniform mixing (compatibility-dispersibility). If the uniform mixing property (compatibility and dispersibility) of the foaming agent and the urethane raw material is low, the reactivity and foaming efficiency (densification) will be reduced, resulting in poor surface finish, reduced strength, In addition to a decrease in dimensional stability and a decrease in heat insulation due to cell roughness, there are problems in that the adhesive strength of the foam to the adherend (casing) is reduced.

[0007] Further, the rigid polyurethane foam based on the water foaming formulation does not have a sufficient adhesive force to the adherend.

[0008] Here, the decrease in the adhesive strength to the adherend is a particular problem in spraying (spraying) performed in a low temperature environment. This decrease in the adhesion strength to the adherend appears remarkably for an extremely low temperature adherend of, for example, -5 ° C, and this solution is particularly required.

[0009] For example, the following methods have been introduced as methods for improving the adhesion of rigid polyurethane foam to an adherend. (1) Number average molecular weight 1550 to 10, 0,000, a hydroxyl group-containing polyether having a monovalent organic group having 3 or more carbon atoms at the end and containing 70% by mass or more of an oxypropylene group A method using isocyanate-terminated prepolymers that have been reacted with (see Patent Document 1). (2) A method using an active hydrogen group-containing polyether that satisfies specific requirements, and an isocyanate group-terminated polymer obtained by reacting an active hydrogen group-containing polysiloxane-polyether copolymer that satisfies specific requirements with isocyanate. 2) (3) A method of introducing an active hydrogen group-free polyether that satisfies specific requirements and / or an active hydrogen group-free polysiloxane-polyether copolymer that satisfies specific requirements into isocyanate (see Patent Document 3). (4) A method of introducing an active hydrogen group-containing polysiloxane-polyether copolymer that satisfies specific requirements into a isocyanate (see Patent Document 4). (5) 3 to 50 carbon atoms A method of using an isocyanate group-terminated polymer obtained by reacting an active hydrogen group-containing hydrocarbon compound and / or an active hydrogen group-containing halogenated hydrocarbon compound having 3 to 50 carbon atoms with an isocyanate (see Patent Document 5). (6) A method of using an isocyanate group-terminated polymer obtained by reacting an active hydrogen group-containing fatty acid ester and / or an active hydrogen group-containing fatty acid amide compound with a isocyanate (see Patent Document 6). (7) Introducing a silicone foam stabilizer into the isocyanate group-terminated polymer obtained by reacting a polyester polyol having a sulfo group or a sulfonate group in the molecular structure with a polyether monool, respectively, with an isocyanate. (See Patent Document 7).

[0010] However, in the conventionally known methods including the methods (1) to (7) above, for example, a hard material having a sufficiently high adhesion to an extremely low temperature adherend of -5 ° C. Polyurethane foam cannot be manufactured.

[001 1] In addition, the polyisocyanate used in the production of rigid polyurethane foam is required to have storage stability of the polyisocyanate at the construction site. Therefore, it is necessary to obtain storage stability in an ultra-low temperature atmosphere of, for example, −5 ° C. in addition to the improvement in adhesion described above.

[0012] Patent Document 1: Japanese Patent Laid-Open No. 2000-2_3 2 2 2 3 1

Patent Document 2: Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 0

Patent Document 3: Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 2

Patent Document 4: Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 3

Patent Document 5: Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 4

Patent Document 6: Japanese Patent Laid-Open No. 2 0 0 2 _ 3 5 6 5 3 5

Patent Document 7: Japanese Patent Laid-Open No. 2 0 0 5 _ 2 1 3 3 0 6

Disclosure of the invention

Problems to be solved by the invention

[0013] The present invention has been made based on the background as described above.

[0014] A first object of the present invention is to obtain a rigid polyurethane foam having good adhesiveness to an extremely low temperature adherend of, for example, -5 ° C and excellent in shape stability. It is an object of the present invention to provide a polyisocyanate composition.

[0015] A second object of the present invention is to provide a polyisocyanate composition for producing a rigid polyurethane foam which is excellent in storage stability even in an ultra-low temperature atmosphere of, for example, -5 ° C.

[0016] A third object of the present invention is to provide good adhesion to an ultra-low temperature adherend of _5 ° C in a foaming formulation using a foamed fluorocarbon and / or water as a foaming agent. And it is providing the manufacturing method of the hard polyurethane foam excellent in the desired mechanical property etc.

[0017] A fourth object of the present invention is to provide a method for producing a rigid polyurethane foam having the above-described excellent performance even by a spray method.

Means for solving the problem

[0018] In order to solve these series of problems (to achieve the object), the present inventors have conducted extensive studies, and as a result, a polyisocyanate composition for producing a rigid polyurethane foam having a specific configuration It has been found that this is very effective as a means for solving the problems, and the present invention has been achieved.

That is, the present invention is as follows (1) to (3).

[0020] (1) (A 1) Diphenylmethane diisocyanate isomer mixture (a 1 d) from 20 to 80 mass ⁰ / o, trinuclear or more diphenylmethane diisocyanate Polymeric MDI in which the polynuclear condensate (a1p) is 80 to 20% by mass (provided that (a1d) + (a1p) = (A1p) = 100 mass ⁰ / o), (A 2) a ricinoleic acid alkyl ester, (A 3) a silicone foam stabilizer that may contain a hydroxyl group, and (A 4) a compound represented by the following general formula (1) And a polyisocyanate composition for producing a rigid polyurethane foam, characterized by being obtained by mixing.

[0021] [Chemical 1]

R ^1- (OR ³ ) n -O- R ² (1) In the above formula, R ¹ and R ² may be the same or different.

A monovalent hydrocarbon group having 1 or more carbon atoms.

R ³ is a divalent divalent having 2 or more carbon atoms of 1 type or 2 types or more

A hydrocarbon group is shown.

n represents an integer of 1 or more.

[0022] (2) The polyisocyanate composition described in (1) is reacted with a polyol (B) in the presence of a blowing agent (C), a catalyst (D) and a foam stabilizer (E). A method for producing a rigid polyurethane foam, characterized in that a hydrofluorocarbon and / or water is used as the foaming agent (C).

[0023] (3) A method for producing a rigid polyurethane foam according to (2), wherein the rigid polyurethane foam is formed on an adherend by a spray method.

The invention's effect

[0024] By using the polyisocyanate composition of the present invention, for example, a hard material having good adhesion to an ultra-low temperature adherend of 15 ° C and having excellent shape stability. Polyurethane foam can be produced.

[0025] Further, since the polysocyanate composition of the present invention is excellent in storage stability even in an ultra-low temperature atmosphere of, for example, -5 ° C, for example, in an ultra-low temperature atmosphere of, for example, 15 ° C. At a certain construction site, it is possible to stably supply a polyisocyanate composition for producing rigid polyurethane foam.

[0026] These excellent effects are further exhibited by good adhesion to super low temperature adherends of _5 ° C in foaming formulations using hide mouth fluorocarbons and / or water as foaming agents. In addition, it is possible to provide a method for producing a rigid polyurethane foam excellent in desired mechanical properties and the like.

[0027] In particular, when a rigid polyurethane foam is formed on an adherend by a spray method, for example, even in construction in an ultra-low temperature atmosphere of -5 ° C, it is desirable. It is sufficiently possible to obtain rigid polyurethane foams that are produced.

BEST MODE FOR CARRYING OUT THE INVENTION

[0028] The present invention will be described in more detail.

[0029] The polyisocyanate composition of the present invention comprises (A 1) diphenylmethane diisocyanate isomer mixture (aid) in an amount of 20 to 80% by mass and a trinuclear or higher diphenylmethane diisocyanate system. Polymeric MD I in which polynuclear condensate (a 1 p) is 80 to 20% by mass (where (aid) + (a 1 p) = (A 1) is 100 mass ⁰ / o), (A 2) An alkyl ricinoleate, (A3) a silicone-based foam stabilizer that may contain a hydroxyl group, and (A4) a compound represented by the following general formula (1):

[0030] [Chemical 2]

R ^1- (0- R ³ ) n -0- R ² (1) In the above formula, RR ² may be the same or different

A monovalent hydrocarbon group having 1 or more carbon atoms.

A hydrocarbon group is shown.

n represents an integer of 1 or more.

[0031] <Polymeric MDI (A 1)> The polymeric MD I (A 1) constituting the polyisocyanate composition of the present invention has an MD I (a 1 d) of 20 to 80% by mass, MD I polynuclear It is a mixture (polyphenylene polymethylene polyisocyanate) in which the condensate (a 1 p) consists of 80 to 20% by mass. The sum of MD I (a 1 d) and M D I polynuclear condensate (a 1 p) is polymeric M D I (A 1

) Is 100% by mass.

[0032] Polymeric MD I (A 1) is obtained by converting the amino group of the condensation mixture (polyamine) obtained by the condensation reaction of aniline and formalin into a silicate group by phosgenation or the like. It is possible to control the composition (nuclear distribution and isomer composition ratio) of the finally obtained polymeric MDI by changing the raw material composition ratio and reaction conditions during the condensation. [0033] The polymeric MD I (A 1) used in the present invention is a reaction solution such as a reaction solution after conversion to an isocyanate group, removal of the solvent from the reaction solution, or a bottom solution obtained by partially distilling and separating MDI. It may be a mixture of several kinds having different conditions and separation conditions. Further, commercially available polymeric MD I may be mixed with MD I (aid).

[0034] The ratio of MD I (a 1 d) in the polymeric MD I (A 1) is in the range of 20 to 80% by mass, preferably in the range of 25 to 75% by mass. Among these, the polymeric MD I (A 1 holding the storage stability of a liquid in), also with a view to including good workability during the rigid poly urethane foam formation, it is particularly preferably in the range of 2 6-70 mass ^_0/0. Here, the ratio of MD I (a 1 d) is a ratio determined from the peak area ratio of MD I by GPC (gel permeation chromatography). Storage stability of polymeric MD I, such as crystal precipitation caused by MD I (a 1 d) when the ratio of MD I (aid) in polymeric MD I (A 1) exceeds 80 mass ⁰ / o However, there is a tendency that the possibility of malfunctions increases. On the other hand, if this ratio is less than 20% by mass, the viscosity of the polymeric MDI tends to be excessively high and there is a high possibility that problems will occur in terms of workability such as poor mixing.

[0035] MD I (aid), a binuclear body, is composed of three isomers: 4, 4 '— MD I, 2, 2' — MD I, and 2, 4 '_MD I. Yes. In the present invention, the composition ratio of these isomers is not particularly limited. However, the above-described conditions more severe than −5 ° C., for example, under severe ambient conditions such as −20 ° C. However, from the viewpoint of excellent storage stability (crystals and the like do not precipitate), the 4,4′_MDI content is preferably in the range of 60 to 95%. The composition ratio of isomers can be obtained from a calibration curve based on the area percentage of each peak obtained by GC (gas chromatography).

[0036] The average number of functional groups of the polymeric MD I (A 1) is preferably 2.2 or more, and more preferably 2.2 to 3.1.

[0037] The isocyanate group content of the polymeric MD I (A 1) is 28 to 33 masses. %, More preferably 28.5 to 32.5% by mass.

[0038] acidity of polymeric MD I (A 1) is preferably a 0.001 to 0.2 mass ^_0/0, is more preferably a 003 to 0.1 5 wt% 0.5. As a result, the storage stability and suitable reactivity of the resulting polyisocyanate composition are ensured. “Acidity” refers to the value obtained by converting the acid component that reacts with alcohol at room temperature to liberate into hydrogen chloride, and is measured according to JIS K-1603.

[0039] The polymeric MDI (A1) constituting the polyisocyanate composition of the present invention has a polyisocyanate composition of the present invention to be described later when the entire polyisocyanate composition is 100% by mass. In the range of 88.0 to 98.95 mass%, taking into account the proportion of introduction in a series of constituents essential for the composition (and thus the desired performance and effects obtained by the introduction of each constituent) Is preferably used.

<Lisinolenic acid alkyl ester (A2)> The ricinoleic acid alkyl ester (A2) used in the present invention is obtained from ricinoleic acid (12-hydroxy-9-octadecenoic acid: mainly obtained from castor oil. Fatty acid (obtained from castor oil fatty acid) and monohydric alcohol (methanol, ethanol, propanol, isopropanol, butanol, hexanol, 2-ethyl hexyl alcohol, decyl alcohol, isodecyl alcohol, tridecyl alcohol, A polyisocyanate composition of the present invention, which is an esterified product (monohydroxycarboxylic acid condensate ester) with pentadecanol, isopentadecanol, stearyl alcohol, isostearyl alcohol, eicosanol, isoeicosanol, etc. Foaming agent (especially It is a component that imparts uniform mixing properties with the hydro mouth fluorocarbons and / or foaming agents comprising water.

[0041] Examples of the ricinoleic acid alkyl esters (A2) include methyl ricinoleate and butyl ricinoleate. Select only one of these It may be used as a mixture of two or more. These compounds include, for example, “U ric H_3 1 (Methyl ricinoleate, manufactured by Ito Oil Co., Ltd.)”, “K_PON 1 80 (Methyl ricinoleate, manufactured by Ogura Synthetic Co., Ltd.)”, “K_PON 1 80 HP (Methyl ricinoleate (high-purity product), manufactured by Ogura Gosei Co., Ltd.) ”and“ K_PON 180 B (Butyl ricinoleate, manufactured by Ogura Gosei Co., Ltd.) ”are available from the market.

[0042] In the present invention, as the ricinoleic acid alkyl ester (A2), the effect of improving uniform mixing with a foaming agent (particularly, a foaming agent composed of a hydro mouth fluorocarbon and / or water) is sufficiently obtained. It is preferable to select and use methyl ricinoleate from the viewpoint that the polyisocyanate composition obtained can be exerted and the viscosity of the resulting polyisocyanate composition is not too high and the possibility of causing a decrease in workability is extremely low.

[0043] The ricinoleic acid alkyl ester (A2) constituting the polyisocyanate composition of the present invention is a polyurethane obtained by the present invention when the entire polyisocyanate composition is 100% by mass. The foam has good dimensional stability (when the introduction amount is excessive, the dimensional stability deteriorates), and the introduction has the desired effect in the polyisocyanate composition of the present invention (introduction amount). From the viewpoint that the effect cannot be obtained when the amount is too small), it is preferably used in the range of 0.5 to 5% by mass.

[0044] In the polyisocyanate composition of the present invention, the ricinoleic acid alkyl esters (A 2) are present in a form reacted with a part of the isocyanate group in the polymeric MD I (A 1). In addition, it may exist in a uniformly mixed form without reacting with the isocyanate group.

<Silicone-based foam stabilizer (A 3)> The silicone-based foam stabilizer (A 3) which may contain a hydroxyl group constituting the polyisocyanate composition of the present invention is not particularly limited. Any conventional foam stabilizer (dimethylpolysiloxane and polysiloxane-polyether copolymer) can be used as the foam stabilizer for the rigid polyurethane foam. [0046] Examples of the silicone foam stabilizer (A3) include known silicone surfactants such as L-5340, L_5420, L manufactured by Toray Dow Corning.

— 5421, L_5740, L_580, S Z_ 1 1 42, S Z-1 642, S Z_ 1 605, S Z_ 1 649, S Z_ 1 91 9, S H_ 1 90, S H

— 1 92, S H_ 1 93, S F_2945 F, S F_2940 F, S F_2 936 F, S F_2938 F, S RX_294A, Shin-Etsu Chemical F_ 3 05, F_341, F_343, F_374, F_345, F_348, Go —Ludschmitt B-8404, B-8407, B-8465, B-8444, B_8467, B_8433, B_8466, B_8870, B_8450, B_8460 and the like.

In the present invention, a polysiloxane-polyether copolymer containing a hydroxyl group (hereinafter referred to as “hydroxyl group-containing silicone”) is used as a part or all of the silicone foam stabilizer (A3). Is preferred. In this case, according to the polyisocyanate composition of the present invention containing a hydroxyl group-containing silicone-based foam stabilizer, uniform mixing with a foaming agent (particularly, hydrofluorocarbons and / or The compatibility with water blowing agents and the dispersibility of the blowing agent in the composition) can be further improved.

[0048] The hydroxyl group-containing silicone is a block copolymer having a dimethylpolysiloxane structure and a polyoxyalkylene structure (polyether structure), and is a compound having a hydroxyl group in the molecular structure.

[0049] The average number of functional groups of the hydroxyl group-containing silicone (average number of hydroxyl groups in one molecule) is preferably 1 to 10, more preferably 1 to 5, particularly preferably "! To 2". If the average number of functional groups is too large, the resulting polyisocyanate composition has a high viscosity, and the workability during foaming tends to decrease.

[0050] The number average molecular weight of the hydroxyl group-containing silicone is preferably 500 to 20,000, and more preferably 1,000 to 18,000. Those having an excessive number average molecular weight have high viscosity and poor handleability.

[0051] The hydroxyl value of the hydroxyl group-containing silicone is 3 to 3 O Omg KOH / g. More preferably, it is 5 to 15 Omg KOH / g. When the hydroxyl value is too small, the viscosity is high and the handling property is inferior, and the formed foam does not have sufficient strength. On the other hand, when the hydroxyl value is excessive, the resulting polyisocyanate composition cannot sufficiently improve the uniform mixing property with the foaming agent.

[0052] When the polyisocyanate composition of the present invention is 100% by mass, the silicone-based foam stabilizer (A3) which may contain a hydroxyl group is from 0.05 to 2.0. It is preferably used in the range of mass%, more preferably in the range of 0.1 to 1.0 mass%, and in particular, it has the liquid viscosity of the polyisocyanate composition of the present invention (increased viscosity due to excessive introduction) In addition, from the standpoint of having uniform mixing (compatibility) with the hydrated fluorocarbons (this effect cannot be obtained with slight introduction), 0.2 to 1.0% by mass It is particularly preferred to be used in a range.

<Compound represented by the following general formula (1) (A4)> The compound (A 4) represented by the following general formula (1) constituting the polyisocyanate composition of the present invention includes: For example, all conventionally known compounds called dialkyl glycol ethers can be used.

[0054] [Chemical 3]

R-(0- R π -0- R (1) In the above formula, R 'may be the same or different.

A monovalent hydrocarbon group having 1 or more carbon atoms.

A hydrocarbon group is shown.

n represents an integer of 1 or more.

[0055] In the present invention, when forming a rigid polyurethane foam, from the viewpoint of imparting better uniform mixing (compatibility) with a polyol or water to the polyisocyanate composition of the present invention, As the compound (A4) represented by the formula (1), diethylene glycol dimethyl ether (DMDG), triethylene glycol dimethyl ether (DMTG), diethylene glycol Examples thereof include coal jetyl ether (DE DG), diethylene glycol dibutyl ether (DBDG), and dipropylene glycol monodimethyl ether (DM F DG). These may be used alone, or 2 More than one species may be used in combination.

[0056] In the present invention, the compound (A4) represented by the general formula (1) has a relatively high boiling point and flash point, a low viscosity, and compatibility with water. From the standpoint of good results, it is preferable to select and use diethylene glycol jetyl ether (DE DG).

[0057] When the polyisocyanate composition of the present invention is 100% by mass, the compound (A4) represented by the general formula (1) is in the range of 0.5 to 5.0% by mass. It is preferably used, and more preferably in the range of 0.5 to 3.0% by mass, and in particular, the desired dimensional stability is ensured for the resulting rigid polyurethane foam. In addition, from the viewpoint of having excellent adhesion under a low temperature atmosphere of, for example, -5 ° C (this effect cannot be obtained if the introduction amount is small). It is particularly preferable to use in the range of 5% by mass.

<Other Isocyanate Compound> The polyisocyanate composition of the present invention contains the above-mentioned polyisocyanate composition.

Meric MD I (A 1) is essential, but if necessary, the polyisocyanate composition of the present invention contains an isocyanate compound other than the essential isocyanate compound (hereinafter referred to as “other isocyanate compound”). Abbreviation.) May be contained.

[0059] Other isocyanate compounds include urethanates obtained by reacting polymeric MD I (or MDI only) and active hydrogen group-containing compounds (the above-mentioned ricinoleic acid alkyl esters (A 2) and polymeric MD I). (Excluding those in the form of a reaction with a part of the isocyanate group in (A 1)), urea compound, allophanate compound, biuret compound, carposimidide compound, ureton iminate product, uretdiionide product, isocyanurate conversion 2,4_tolylene diisocyanate, 2,6_tolylene diisocyanate, xylene-1,4-diisocyanate, xylene_1,3-diisocyanate, tetramethylxylene diisocyanate, m —Aromatic diisocyanates such as phenylene diisocyanate, p-phenylene diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, 3_methyl-1,1,5_pentanediisocyanate, lysine Aliphatic diisocyanate such as diisocyanate; cyclophore such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate A group dissociator. Urethanes, ureas, allophanates, biuretates, carposimidides, uretoniminates, uretdiionides, isocyanurates obtained by reacting these polymeric substances and these isocyanates with active hydrogen group-containing compounds. Chemicals can also be used. These isocyanate compounds can be used alone or in combination of two or more.

<Optional Components> [0060] The polyisocyanate composition of the present invention may contain various optional components as long as the effect is not impaired. As such optional components, all of the conventionally known substances (additives, etc.) that are contained in the polyisocyanate composition for producing a rigid polyurethane foam can be used.

[0061] <Polyisocyanate composition> The isocyanate group content in the polyisocyanate composition of the present invention is preferably 28.0 to 31.5% by mass, more preferably 28.5 to 31.0% by mass, in particular, the mechanical properties desired for the rigid polyurethane foam obtained by using the polyisocyanate composition of the present invention can be provided. From the viewpoint that the viscosity of the isocyanate composition is suitable for the production of a rigid polyurethane foam (for example, spraying operation at the time of spray foaming), it is particularly preferably 29.0 to 31.0% by mass. [0062] The viscosity (25 ° C) of the polyisocyanate composition of the present invention is preferably 50 to 50 OmPa · s, more preferably 70 to 300 mPa · s, among which rigid polyurethane foam 80 to 150 mPa · s is particularly preferable from the viewpoint of being suitable for the production of (for example, spraying work during spray foaming).

[0063] The polyisocyanate composition of the present invention is excellent in homogeneous mixing with the hydro mouth fluorocarbons and water (compatibility / hydrofluorocarbons and water dispersibility in the composition). Therefore, it is preferably used for producing a rigid polyurethane foam by a foaming formulation using these as a foaming agent.

[0064] The polyisocyanate composition of the present invention is particularly suitable for use in a low-temperature environment in which a conventionally known polyisocyanate composition cannot be applied from the viewpoint of adhesion, particularly in a very low-temperature environment such as _5 ° C. It can be applied in spraying construction (spray construction), and a rigid polyurethane foam having good adhesion to the adherend can be formed.

[0065] Here, the adherend to which the polyisocyanate composition of the present invention is applied is not particularly limited, and examples thereof include woods, concretes, various metals, papers, and stones. And various plastics, ceramics, glasses, and various rubbers.

[0066] As a matter of course, the usage mode (construction method) of the polyisocyanate composition of the present invention is not limited to spray construction.

<Manufacturing Method of Rigid Polyurethane Foam> The manufacturing method of the present invention comprises the above-described polyisocyanate composition of the present invention and a polyol (B), a foaming agent (C), a catalyst (D) and an adjusting agent. A method for producing a rigid polyurethane foam that is reacted in the presence of a foaming agent (E), wherein the polyisocyanate composition comprises (A 1) a diphenylmethane disoocyanate isomer mixture (aid) 20-80% by mass, 3 or more nuclei of diphenylmethane di iso Xia sulfonate-based polynuclear condensate (a 1 p) is 80 to 20 mass ^_0/0 (where, (aid) + (a 1 p) = ( Polymeric MD I which is 100 mass ⁰ / o) as A1), (A2) alkyl ricinoleate Production of rigid polyurethane foam obtained by reacting and mixing an ester, (A3) a silicone-based foam stabilizer that may contain a hydroxyl group, and (A4) a compound represented by the following general formula (1) And is characterized by the use of hydrofluorocarbon and / or water as the foaming agent (C).

[0068] [Chemical 4]

R ¹ — (O— n -0- (1) In the above formula, R ¹ and R ² may be the same or different.

A monovalent hydrocarbon group having 1 or more carbon atoms.

A hydrocarbon group is shown.

n represents an integer of 1 or more.

<Polyol (B)> The “polyol (B)” used in the production method of the present invention is not particularly limited, and examples thereof include conventionally known polyester polyols, polyether polyols, and polycarbonate polyols. I can do it. In consideration of the strength of the rigid polyurethane foam to be formed, a low molecular polyol, a low molecular polyamine, a low molecular amino alcohol or the like may be used in combination.

[0070] As the polyol (B) used in the production method of the present invention, it is preferable to use at least one of the following three types of polyols [polyols (b 1) to (b 3)]. It is more preferable to use the above.

[0071] When only one of polyol (b 1) and polyol (b 3) is used, the formed rigid polyurethane foam may not have sufficient mechanical strength. Polyol (B) consisting only of polyol (b 2) tends to be inferior in workability due to excessive viscosity.

[0072] [Polyol (b 1)] Monoethanolamine, diethanolamine, alkanolamines such as trietanolamine, tolylenediamine, ethylendiamine, diethylenetriamine, ammonia, aniline, xylylenediamine, diaminodiphenyl Of amine compounds such as polyamines such as rumethane Hydroxyl group value 50 ~ "!, OO Omg KOH / g, obtained by addition reaction of alkylene oxides such as ethylene oxide and propylene oxide using one or a mixture of two or more as initiators Preferably, polyether polyol of 100 to 900 mg KO H / g In addition, a polyhydric alcohol used for obtaining polyol (b 2) and polyol (b 3) can be used in combination as an initiator.

[Polyol (b 2)] (1) Ethylene glycol, propanediol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3 _Methyl mono 1,5_ A mixture of one or more polyhydric alcohols such as pentanediol, glycerin, trimethylolpropane, pentaerythritol and adipic acid, malonic acid, fumaric acid, oxalic acid, tartaric acid, oxalic acid Of compounds having at least two or more strong lpoxyl groups (or groups derived from strong lpoxyl groups), such as phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarponic acid, etc. 1 type or 2 types or more A polyester polyol having a hydroxyl value of 50-80 Omg K OH / g, preferably 100-700 mg K OH / g, which is obtained by production by a known method. (2) A polyester polyol obtained by ring-opening polymerization of lactone (for example, pro-lactone). (3) Recovered polyester obtained by decomposing polyester polyol and polyester molded product.

[0074] [Polyol (b 3)] Ethylene glycol, propanediol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3_methyl 1 1,5_Pentanediol, Glycerin, Trimethylolpropane, Pentaerythri! The initiator is a polyhydric alcohol having 2 to 6, preferably 2 to 5 hydroxyl groups in one molecule. Hydroxyl value 50 ~ obtained by addition reaction of alkylene oxides such as

1, O O Omg KOH / g, preferably 100 to 900 mg KOH / g of a polyester monopolyol.

[0075] In each of the polyols (b 1) to (b 3), when the hydroxyl value is a certain value (lower limit) or more, sufficient mechanical strength can be imparted to the formed rigid polyurethane foam. it can. Further, when the hydroxyl value is not more than a certain value (upper limit value), brittleness of the formed rigid polyurethane foam can be suppressed.

[0076] The average number of functional groups of the polyol (b 1) is preferably 2 to 8, and more preferably 3 to 6.

[0077] The average number of functional groups of the polyol (b 2) is preferably 2 to 4, more preferably 2 to 3.

[0078] The average number of functional groups of the polyol (b 3) is preferably 3 to 6, and more preferably 3 to 5.

[0079] In each of the polyols (b 1) to (b 3), when the average number of functional groups is a certain number (lower limit) or more, sufficient mechanical strength can be imparted to the formed rigid polyurethane foam. it can. In addition, when the average number of functional groups is a certain number (upper limit) or less, embrittlement of the formed rigid polyurethane foam can be suppressed.

[0080] When the polyol (b 1) is used, the proportion of the polyol (b 1) in the polyol (B) is preferably 40 to 70% by mass.

[0081] When the polyol (b 2) is used, the proportion of the polyol (b 2) in the polyol (B) is preferably 10 to 90% by mass.

[0082] When the polyol (b 3) is used, the proportion of the polyol (b 3) in the polyol (B) is preferably 10 to 70% by mass.

[0083] The total proportion of polyol (b 1), polyol (b 2) and polyol (b 3) in the polyol (B) is preferably 80% by mass or more.

[0084] If the content ratio of the polyol (b 1) is excessively high, the activity becomes too high. There is a risk of molding defects such as

[0085] When the content ratio of the polyol (b 2) is excessive, the viscosity of the polyol (B) increases and the liquid flowability and filling property of the foam tend to deteriorate.

[0086] If the content ratio of the polyol (b 3) is excessive, the mechanical strength of the hard polyurethane foam formed tends to decrease.

[0087] Polyols other than the polyols (b 1) to (b 3) constituting the polyol (B) (hereinafter abbreviated as "polyols") include ethylene glycol, diethylene glycol, and hydroxyl values of 50 to 15 Om. A suitable example is polypropylene glycol of g KO H / g.

[0088] By using at least one selected from ethylene glycol, diethylene glycol, and polypropylene glycol having a hydroxyl value of 50 to 150 mg KOH / g, the viscosity of the polyol (B) can be reduced.

Monkey.

[0089] In addition, a polymer polyol may be used as the other polyol constituting the polyol (B). This polymer polyol is based on the above-mentioned polyether polyol or polyester polyol, and a vinyl polymer of styrene or acrylonitrile, or a polymer obtained from an active hydrogen group-containing compound and polyisocyanate として is introduced as a graft polymerization or filler. Is. The polymer content in the polymer polyol is preferably 1 to 20% by mass.

[0090] The viscosity (25 ° C) of the polyol (B) is preferably 2,000 OmPa-s or less, and more preferably from 100 to 1,800 mPas. When the viscosity exceeds the upper limit, workability particularly in winter is reduced.

<Foaming agent (C)> In the production method of the present invention, hydrofluorocarbon and / or water are used as the foaming agent (C).

[0092] The amount of foaming agent (C) to be added should be the following when using a high mouth fluorocapon such as H FC_245 fa, HF C-365m fc, H FC_ 1 34 a, etc. (B) against a 50 mass ^_0/0. [0093] In addition, the amount of water added in the case of using the combined hydrofluorocarbon and water is 0.5 to 5.0% by mass with respect to the polyol (B).

[0094] Further, in the complete water foam formulation using water only, the amount of water added, 2. a 0 to 20.0 mass ^_0/0 for polio one Le (B).

[0095] In the present invention, as the foaming agent (C), a combined use of a hydro mouth carbon and water, specifically, the main foaming agent is hydrofluorocarbon and the secondary foaming agent is used as water. The form exerts the most desired effect on the rigid polyurethane foam obtained by the production method of the present invention. Here, “primary foaming agent” and “secondary foaming agent” are some of the mass parts used, and “primary foaming agent” is more mass part than “secondary foaming agent”. In meaning

[0096] In the production method of the present invention, desired performance (for example, dimensional stability (small shrinkage at room temperature)) and adhesion to an adherend (for example, -5 ° C) are obtained in the obtained rigid polyurethane foam. If it is within a range that can maintain good adhesion even in a low-temperature atmosphere), it is possible to use hydro mouth fluoro ether as a foaming agent (C) in combination with hydro fluorocapon and / or water. Is possible.

[0097] As the Hide mouth Fluorotel, there is a conventionally known one as the Hyde mouth Fluorotel, for example, H FE-254 pc (CH F ₂ CF ₂ OCH ₃ ), CF ₃ CH FOC F ₃ (H FE— 227me), CF ₃ CH FOCH F ₂ (H FE-236me), CF ₃ CH ₂ OC F ₃ (H FE-236m f), CHF ₂ CF ₂ OCH F ₂ (H FE-236 pc) , CF ₃ CF ₂ OCH ₃ (H FE—

245 mc), CF ₃ CH ₂ OCH F ₂ (H FE-245m f), CF ₃ CF ₂ CF ₂ OCH ₃ (H FE-247mc c), CF ₃ CF ₂ OCH ₂ CF ₃ (H FE—

338 mc-f), (CF ₃ ) ₂ C FOCH ₃ (HF E- 347 mm y), CHF ₂ CF ₂ OCH ₂ F (H FE-245 pc), CH ₂ FC F ₂ OCH F ₂ (HF E- 245 qc), CF ₃ CF ₂ CH ₂ OCH F ₂ (H FE_347mc f), CF ₃ CH FC F ₂ OCH ₃ (H FE-356me c), CH F ₂ CF ₂ CF ₂ 0 CH ₃ (HF E-356 pcc), CH F ₂ CF ₂ CH ₂ OCH F ₂ (HFE— 3 56 pcf), CH F ₂ CF ₂ OCH ₂ CF ₃ (HF E_347 pc _ f), CF ₃ CH ₂ OCH ₂ CF ₃ (HF E-356 m f-f), CH ₂ FC F ₂ OCH ₂ CF ₃ (HF E-356 qc-f), (CF ₃ ) ₂ CHOCH ₃ (HFE— 35 6 mm z), etc. Can do. In the production method of the present invention, any one of these may be selected and used in combination with a hydrofluorocapon and / or water, or two or more of these may be used in combination. It may be used in combination with a forceful pump and / or water.

<Catalyst (D)> As the “catalyst (D)” used in the production method of the present invention, a known catalyst usually used for urethane foaming can be used. For example, N-methylimidazole, trimethylaminoethyl piperazine, tripropylamine, tetramethylhexamethylenediamine, triethylenediamine, triethylamine, N-methylmorpholine, dimethylcyclohexane Examples thereof include tin compounds such as hexylamine, dibutyltin diacetate and dibutyltin dilaurate, and metal complex compounds such as acetylethylaceton metal salt. Trimerization catalysts include 2, 4, 6-tris (dimethylaminomethyl) phenol, 1, 3, 5-tris (dimethylaminopropyl) hexahydro _ s-triazines such as triazine, 2, 4_bis (Dimethylaminomethyl) Phenyl, 2-ethylhexyl hexanoate, 2-ethylhexyl sodium acetate, potassium acetate, sodium acetate, amine compounds such as aziridines such as 2-ethylaziridine, tertiary Quaternary ammonium compounds such as carboxylic acid salts of amines, lead compounds such as diazabicycloundecene, lead naphthenate and lead octylate, alcoholic compounds such as sodium methoxide, potassium phenoxide And the like, and the like. These catalysts can be used alone or in combination of two or more.

[0099] The amount of the catalyst (D) used is suitably from 0 to 1 to 15% by mass based on the polyol (B).

[0100] <Foam stabilizer (E)> As the foam stabilizer (E) used in the production method of the present invention, The above-mentioned silicone-based foam stabilizer (A 3) is not particularly limited, and conventionally known foam stabilizers for rigid polyurethane foam (dimethylpolysiloxane and polysiloxane-polyether copolymer) are used. All can be used. Specific examples thereof include those listed in the aforementioned silicone foam stabilizer (A 3). The amount of the foam stabilizer (E) used is suitably 0.1 to 5% by mass relative to the polyol (B). In addition, the foam stabilizer (E) used in the production method of the present invention has the performance desired for the rigid polyurethane foam obtained by the present invention, and the aforementioned silicone foam stabilizer (A 3). The same one as that used in the above may be used, or another one may be used.

[0101] In the production method of the present invention, an additive can be used (the polyisocyanate mixture (A) and the polyol (B) are reacted in the presence of the additive). Examples of these additives include plasticizers, fillers, colorants, flame retardants, organic or inorganic fillers, antioxidants, UV absorbers, plasticizers, pigments, dyes, antibacterial agents, and antifungal agents. . In the present invention, it is preferable to use a flame retardant. Examples of the flame retardant include phosphate esters such as triethyl phosphate and tris (S-clopropyl) phosphate, and phosphate compounds of phosphites such as ethyl phosphite and jetyl phosphite. It is done.

[0102] In the production method of the present invention, a multi-component system having three or more components may be used. However, for the purpose of simplifying the apparatus, the "I liquid" containing the polyisocyanate composition of the present invention as a main component. And a two-component system consisting of an “R liquid” composed mainly of the polyol (B).

[0103] Examples of preferred specific production methods in the case of a two-component system are shown below.

(1) The polyisocyanate composition of the present invention is referred to as “Liquid I”, and the polyol (B) is referred to as “R liquid”.

(2) The foaming agent (C), the catalyst (D), the foam stabilizer (E) and the additive (optional component) are mixed in the “I liquid” and / or “R liquid”. The foaming agent (C), catalyst (D) and foam stabilizer (E) are preferably mixed in the “R liquid”. In addition, the silicone-based foam stabilizer (A 2) contained in “Liquid I” from the beginning is handled as a constituent of the foam stabilizer (E) in the subsequent steps.

(3) “Liquid I” and “R-liquid” are mixed, and the polyisocyanate composition of the present invention and the polyol (B) are mixed with the foaming agent (C), The reaction is carried out in the presence of a catalyst (D) and a foam stabilizer (E), and the reaction system is foamed and cured.

[0107] The mixing device for "I liquid" and "R liquid" is not particularly limited. For example, it is used for the production of small mixers and general urethane foam. Low pressure or high pressure foaming machines, low pressure or high pressure foaming machines for slab foaming, low pressure or high pressure foaming machines for continuous lines, spray foaming machines for spraying work, etc. can be used. The temperature of the “I liquid” and “R liquid” to be mixed is preferably adjusted to 15 to 50 ° C.

[0108] The rigid polyurethane foam obtained by the production method of the present invention has a chemical bond such as a urethane bond or urea bond (so-called urethane foam). In addition, depending on the production conditions, isocyanurate groups can be generated at the time of foaming, and isocyanurate-modified polyurethane foams (so-called isocyanurate foams) thus obtained are also included in “rigid polyurethane foam”. . The isocyanurate group is formed by trimerizing the isocyanate group with a trimerization catalyst, and can improve mechanical strength, heat resistance, and the like.

In the production method of the present invention, a preferred isocyanate index [(number of moles of all isocyanate groups in the polyisocyanate composition / number of moles of all active hydrogen groups in the polyol (B)) X 1 0 0] is In the case of so-called urethane foam, it is preferably from 50 to 140, and more preferably from 70 to 130. In the case of so-called isocyanurate foam formed using a trimerization catalyst, it is preferably from 140 to 800, more preferably from 150 to 500. When the isocyanate index is urethane foam 5 0 If it is less than 140 in the case of isocyanurate foam, the resulting foam may not have sufficient strength and is likely to shrink. In the case of urethane foam, exceeding 140, and in the case of isocyanurate foam exceeding 800, the resulting foam tends to become brittle and the adhesiveness tends to decrease.

[0110] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples. In the following, unless otherwise specified, “%” and “part” indicate “% by mass” and “part by mass”, respectively.

[0111] <Synthesis of Organic Polyisocyanate Composition> Example 1: In accordance with the formulation shown in Table 1 below, a reactor having a capacity of 100 kg equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe, and a thermometer was 84.7 kg of “Isocyanate B” and 1 1.6 kg of “Isocyanate D” were charged, respectively, and heated to 60 ° C. with stirring to obtain “Polymeric MD I (A 1)”. . Next, 2. O kg of “A2_1” as the alkyl ester of ricinoleic acid (A2) and 0.2 kg of “A3_2” as the silicone foam stabilizer (A 3), dialkylglycol ester ( As A4), 1.5 kg of “A4_1” was charged into each reactor. After completion of preparation, the reaction is carried out at 60 ° C for 2 hours with stirring, and the polyisocyanate assembly of the present invention

The product “N C O _ 1” was obtained. The isocyanate group content (hereinafter abbreviated as “NCO content”, if necessary) of this polyisocyanate composition “NCO _ 1” is 29.6%, and the viscosity (25 ° C) is 1 21 mP a ■ s Met.

[0112] Examples 2 to 18, Comparative Examples 1 to 9: In accordance with the formulations shown in Table 1 and Table 2 below, isocyanate A to D, ricinoleic acid alkyl esters (A2) as "A2_1" or "A2_2" Except for using “A3_1” or “A3-2” as the silicone-based foam stabilizer and each of “A4_1” to “A4_5” as the dialkyl glycol ether (A4), Example 1 and Similarly, polyisocyanate compositions “NCO_2” to “NCO — 18” of the present invention and polyisocyanate compositions “NCO — 19” to “NCO — 27” as comparative examples were prepared. The isocyanate content and viscosity (25 ° C) of the obtained polyisocyanate composition are shown in Tables 1 to 5 together.

<0113] <Hydrogenocarbons and homogeneous mixing with water> Polyisocyanate compositions “NC 0_ 1” to “NCO_27” obtained in Examples 1 to 18 and Comparative Examples 1 to 9 above For each of the above, the homogeneous mixing with the hide mouth fluorocarbons and water was evaluated according to the following method. The results are also shown in Tables 1 to 5.

[0114] (Evaluation Method for Uniform Mixability with Hydrofluorocarbons) Polyisocyanate composition 50 g and Hydrofluorocapon (H FC_365m fc) 20 g were charged into a laboratory mixer, 7, The mixing operation was performed at 000 rpm for 3 seconds, and the appearance of the mixture was observed visually immediately after the operation and after 30 minutes, and evaluated based on the following criteria.

[0115] (Evaluation method for homogeneous mixing with water) Polyisocyanate (composition) 50 g and purified water 5 g were charged into a laboratory mixer and mixed at 7,000 rpm for 3 seconds. Immediately after the operation and after 30 minutes, the appearance of the mixture was visually observed and evaluated based on the following criteria.

[0116] (Evaluation criteria) “「 ”: A homogeneous emulsified state was obtained, and this state was maintained even after 30 minutes. “◯”: An emulsified state was obtained, but phase separation occurred after 30 minutes. “X”: Phase separation occurred immediately after the operation.

[0117] <Liquid Storage Stability of Polyisocyanate Composition in Low Temperature Atmosphere> Polyisocyanate composition “NCO — 1” obtained by Examples 1 to 18 and Comparative Examples 1 to 9 above For each “NCO_27”, 200 g in a 200 ml glass sample bottle was sealed, sealed with a lid, and then left for 90 days at _5 ° C, -10 ° C, and -20 ° C. . The appearance after 90 days was visually observed and evaluated based on the following criteria. The results are also shown in Tables 1 to 5. [0118] (Evaluation Criteria) “◯”: No crystal precipitation or liquid phase separation is observed. “X”: Crystal precipitation, liquid phase separation, or liquid turbidity that seems to be a precursor of these. The above polyisocyanate compositions “NCO — 1” to “NCO-27J” at the start of measurement are all judged to be “◯”.

[0119] [Table 1]

[0120] Ho 2]

[0121] 3

[0122] [Table 4]

[0123]

5

[0124] The details of the compounds (components or reaction raw materials) in Tables 1 to 5 are as follows. The unit of these usages is “parts”.

[0125] Isocyanate A> (i) MPC peak area ratio by GPC = 40% (polymeric MD I), (ii) 4, 4 '— MD I ratio in MD I = 99% (GC ) (Iii) Isocyanate content = 30.8 <½, (iv) Average number of functional groups = 2.3, (V) Acidity = 0.01 <½. <Isocyanate B> (i) MPC peak area ratio by GPC = 37% (polymeric MD I), (ii) 4, 4'_MD I ratio in MD I = 89% (measured by GC) (Iii) Isocyanate content = 30.7%, (IV) Average number of functional groups = 2.3, (V) Acidity = 0.01%. Isocyanate C> (i) MD I (binuclear), (ii) 4, 4'_MD I ratio = 99 <½ (measured by GC), (iii) acidity = 0.001%. Isocyanate D> (i) MD I (binuclear), (ii) 4, 4 '— Percentage of MDI = 82% (determined by GC), (iii) Acidity = 0.0010 / 6. <Lisinoleic acid alkyl esters (A2-1)> Methyl ricinoleate “U ric H_31” (manufactured by Ito Oil Co., Ltd.). <Lisinolenic acid alkyl esters (A2-2)> Methyl ricinoleate “K_PON 1 80” (manufactured by Ogura Gosei Kogyo Co., Ltd.). <Silicone-based foam stabilizer (A3-1)> Polysiloxane-polyether copolymer “L-5340” (manufactured by Toray Dow Corning Co., Ltd.), hydroxyl value = 0. <Silicone-based foam stabilizer (A3-2)> Polysiloxane-poly Ether copolymer “B_8460” (manufactured by Goldschmidt), hydroxyl value = 120. <Dialkyl glycol ether (A4-1)> Jetyl diglycol (diethylene glycol jetyl) "DEDG" (manufactured by Nippon Emulsifier Co., Ltd.). <Dialkylglycol ether (A4-2)> Dimethyltriglycol (triethyleneglycoldimethylether) “DMTG” (manufactured by Nippon Emulsifier Co., Ltd.). <Dialkyl glycol ether (A4-3)> Diethylene glycol dimethyl ether "DMDG" (manufactured by Nippon Emulsifier Co., Ltd.). <Dialkylglycol ether (A4-4)> Diethylene glycol dibutyl ether "DBDG" (manufactured by Nippon Emulsifier Co., Ltd.). <Dialkyl glycol monoether (A4-5)> Dipropylene glycol dimethyl ether "DM FDG" (manufactured by Nippon Emulsifier Co., Ltd.). <Specific Polyester Polyol> (i) 5_ Sodium sulfoisophthalate dimethyl, adipic acid, 1,6-hexandiol reacted in the usual way (ester reaction and transesterification) Group (sodium sulfonate residue) -containing abbit polyester polyol, (ii) number average molecular weight = 1,000, sulfonate group content ratio = 0.4 mmol / g.

<0126] <Preparation Examples 1 and 2> According to the formulation shown in Table 3 below, the polyol compositions “OH_1” and “OH_2” were prepared by uniformly mixing each component.

[0127] [Table 6]

[0128] Details of the compounds (components) in Table 5 above are as follows. The unit of these usages is “parts”. <Polyol (B_1)> Polyester polyol “terol 693” (manufactured by OXID, USA) having a hydroxyl value of 250 using phthalic anhydride / diethylene glycol as a raw material. <Polyol (B-2)> Polyester polyol “terol 2500” (manufactured by OX ID, USA) having a hydroxyl value of 250 using phthalic anhydride / diethylene glycol as a raw material. <Polyol (B-3)> Mannich polyether polyol “DK polyol 3776” having a hydroxyl value of 350 (Daiichi Kogyo Seiyaku Co., Ltd.). <Polyol (B-4)> Mannich polyether polyol “DK polyol 3773” (Daiichi Kogyo Seiyaku Co., Ltd.) having a hydroxyl value of 450. <Foaming agent (C_ 1)> H FC-245 fa (manufactured by Central Glass Co., Ltd.). <Foaming agent (C_2)> H FC-365m fc (manufactured by Solvay). <Foaming agent (C_3)> Purified water. <Catalyst (D_ 1)> Trimerization catalyst “DABCO K 1 5” (manufactured by Air Products). <Catalyst (D-2)> Lead octylate "Nikka Octix Lead" (manufactured by Nippon Chemical Industry Co., Ltd.). <Foam stabilizer (E-1)> Polysiloxane-polyether copolymer “B_8460” (manufactured by Goldschmitt). <Flame Retardant (F-1)> Tris (; 3-propyl propyl) phosphate "Fairoll PC F" (manufactured by Akzo Nobel).

<Formation of Rigid Polyurethane Foam (Production)> Example 1 9 to 37, Comparative Example 1 0 to 18: According to the combinations shown in Table 7 to Table 11 below, polyisocyanate composition (Liquid A) And a liquid composition (mixing volume ratio = 100: 1 00) with a polyol composition (Liquid B) on a plywood plate (1 00 OmmX 1 00 Omm) on which an image paper (50 mm x 50 mm) as an adherend is affixed ) To make the polyisocyanate mixture (A) react with the polyol (B) in the presence of the foaming agent (C), catalyst (D), foam stabilizer (E), etc. A rigid polyurethane foam was formed on the entire surface of the plywood (1 OO OmmX l 00 Omm) to which the adherend was applied. The cream time and rise time were measured as reactivity during the formation. The foam core density was measured after curing in a 15 ° C atmosphere while standing for 24 hours. Here, the blowing and foaming conditions are as follows. ■ Foaming machine: Gasmer spraying foamer "FF — 1 600 ”, ■ Temperature of adherend: _5 ° C, ■ Primary heater temperature: 45 ° C, ■ Foam thickness: 30-4 Omm.

[0131] <Room-temperature shrinkage of foam (volume change rate by leaving)> Example 1 Rigid polyurethane foam formed on plywood (1 00 OmmX 1 00 Omm) according to 9-37 and Comparative example 10 0-18 Samples of length = 10 Omm, width = 100 mm, height (foaming direction) = 25 mm were taken from each of the samples, and this sample was left for 24 hours at a temperature of 25 ° C. ■ By measuring the height dimension again, the volume change rate of the foam was measured and evaluated based on the following criteria. The results are also shown in Table 7 to Table 11.

[0132] (Evaluation criteria) “◎”: Volume change rate = 2 <½. “◯”: Volume change rate = 2% or more and less than 5%. “X”: Volume change rate = 5% or more.

[0133] <Adhesiveness to adherends> Hard polyurethane foam formed on adherends (5 Omm x 5 Omm drawing paper) according to Examples 19 to 37 and Comparative Examples 10 to 18 Each of these was allowed to stand in a temperature environment of _5 ° C for 2 hours and then subjected to a pilling test to measure the adhesive strength to the adherend (drawing paper). The results are also shown in Table 7 to Table 11.

[0134] [Table 7]

[0135] [Table 8]

[0136] 9

[0137] [Table 10]

[0138] [Table 1 1]

Industrial applicability

[0139] The polyisocyanate composition of the present invention comprises a board, a panel, a refrigerator, a firewood, a door, a shutter, a sash, a concrete house, a bathtub, a cryogenic tank device, a freezer warehouse, a pipe cover, anti-condensation, a slab, etc. It can be applied to various insulation materials.

[0140] The polyisocyanate composition of the present invention is applied to various adherends by spraying.

(Spray foaming), especially suitable for spraying applications (spray foaming) on various substrates in cold regions, for example at temperatures of 1-5 ° C

Claims

Claim (A 1) Diphenylmethane diisocyanate isomer mixture (aid) 20 to 80 mass 0/0, trinuclear diphenylmethane diisocyanate polynuclear condensate ( Polymeric MD I in which a 1 p) is 80-20 mass 0 / o (where (a 1 d) + (a 1 p) = 100 mass 0 / o as (A 1)), (A 2) Lisinolein Acid alkyl esters, (A3) a silicone-based foam stabilizer that may contain a hydroxyl group, and (A4) a compound represented by the following general formula (1):

[Chemical 1]

R (0— R ³ ) n −0- R = (1) In the above formula, F and R ² may be the same or different.

A monovalent hydrocarbon group having 1 or more carbon atoms.

A hydrocarbon group is shown.

n represents an integer of 1 or more. A polyisocyanate composition for producing a rigid polyurethane foam, which is obtained by reacting and mixing.

[2] A rigid polyisocyanate composition obtained by reacting the polyisocyanate composition according to claim 1 with a polyol (B) in the presence of a foaming agent (C), a catalyst (D) and a foam stabilizer (E). A method for producing a urethane foam, characterized by using hydrofluorocarbon and / or water as the foaming agent (C).

[3] The method for producing a rigid polyurethane foam according to claim 2, wherein the rigid polyurethane foam is formed on the adherend by a spray method.